Trisilylamine derivatives as precursors for high growth rate silicon-containing films

ABSTRACT

Described herein are compositions and methods for forming silicon and oxygen containing films. In one aspect, the film is deposited from at least one precursor, wherein the at least one precursor selected from the group consisting of Formulae A and B:wherein R, R1, and R2-8 are as defined herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application number16/134,108, filed on Sep. 18, 2018, which in turn claims priority under35 U.S.C. § 119(e) to U.S. provisional patent application No.62/560,547, filed on Sep. 19, 2017, the entirety of which bothapplications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

Described herein is a composition and method for the formation of asilicon and oxygen containing film. More specifically, described hereinis a composition and method for formation of a stoichiometric or anon-stoichiometric silicon oxide film or a stoichiometric or anon-stoichiometric silicon nitride film or material at one or moredeposition temperatures of about 300° C. or less, or ranging from about25° C. to about 300° C.

Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic LayerDeposition (PEALD) are processes used to deposit silicon oxide conformalfilm at low temperature (<500° C.). In both ALD and PEALD processes, theprecursor and reactive gas (such as oxygen or ozone) are separatelypulsed in certain number of cycles to form a monolayer of silicon oxideat each cycle. However, silicon oxide deposited at low temperaturesusing these processes may contain levels of impurities such as, withoutlimitation, nitrogen (N) which may be detrimental in certainsemiconductor applications. To remedy this, one possible solution is toincrease the deposition temperature to 500° C. or greater. However, atthese higher temperatures, conventional precursors employed bysemi-conductor industries tend to self-react, thermally decompose, anddeposit in a chemical vapor deposition (CVD) mode rather than an ALDmode. The CVD mode deposition has reduced conformality compared to ALDdeposition, especially for high aspect ratio structures which are neededin many semiconductor applications. In addition, the CVD mode depositionhas less control of film or material thickness than the ALD modedeposition.

The reference article entitled “Some New Alkylaminosilanes,” Abel, E.W.et al., J. Chem. Soc., (1964), Vol. 26, pp. 1528-1530 describes thepreparation of various aminosilane compounds such as Me₃SiNHBu-iso,Me₃SiNHBu-sec, Me₃SiN(Pr-iso)₂, and Me₃SiN(Bu-sec)₂ wherein Me=methyl,Bu-sec=sec-butyl, and Pr-iso=isopropyl from the direct interaction oftrimethylchlorosilane (Me₃SiCl) and the appropriate amine.

The reference article entitled “SiO₂ Atomic Layer Deposition UsingTris(dimethylamino)silane and Hydrogen Peroxide Studied by in SituTransmission FTIR Spectroscopy,” Burton, B. B., et al., The Journal ofPhysical Chemistry (2009), Vol. 113, pp. 8249-57 describes the atomiclayer deposition (ALD) of silicon dioxide (SiO₂) using a variety ofsilicon precursors with H₂O₂ as the oxidant. The silicon precursors were(N,N-dimethylamino)trimethylsilane) (CH₃)₃SiN(CH₃)₂,vinyltrimethoxysilane CH₂CHSi(OCH₃)₃, trivinylmethoxysilane(CH₂CH)₃SiOCH₃, tetrakis(dimethylamino)silane Si(N(CH₃)₂)₄, andtris(dimethylamino)silane (TDMAS) SiH(N(CH₃)₂)₃. TDMAS was determined tobe the most effective of these precursors. However, additional studiesdetermined that SiH* surface species from TDMAS were difficult to removeusing only H₂O. Subsequent studies utilized TDMAS and H₂O₂ as theoxidant and explored SiO₂ ALD in the temperature range of 150-550° C.The exposures required for the TDMAS and H₂O₂ surface reactions to reachcompletion and were monitored using in situ FTIR spectroscopy. The FTIRvibrational spectra following the TDMAS exposures showed a loss ofabsorbance for O—H stretching vibrations and a gain of absorbance forC—Hx and Si—H stretching vibrations. The FTIR vibrational spectrafollowing the H₂O₂ exposures displayed a loss of absorbance for C—Hx andSi—H stretching vibrations and an increase of absorbance for the O—Hstretching vibrations. The SiH* surface species were completely removedonly at temperatures >450° C. The bulk vibrational modes of SiO₂ wereobserved between 1000-1250 cm⁻¹ and grew progressively with number ofTDMAS and H₂O₂ reaction cycles. Transmission electron microscopy (TEM)was performed after 50 TDMAS and H₂O₂ reaction cycles on ZrO₂nanoparticles at temperatures between 150-550° C. The film thicknessdetermined by TEM at each temperature was used to obtain the SiO₂ ALDgrowth rate. The growth per cycle varied from 0.8 Å/cycle at 150° C. to1.8 Å/cycle at 550° C. and was correlated with the removal of the SiH*surface species. SiO₂ ALD using TDMAS and H₂O₂ should be valuable forSiO2 ALD at temperatures >450° C.

JP 2010275602 and JP 2010225663 disclose the use of a raw material toform a Si containing thin film such as, silicon oxide, by a chemicalvapor deposition (CVD) process at a temperature range of from 300-500°C. The raw material is an organic silicon compound, represented byformula: (a)HSi(CH₃)(R¹)(NR²R³), wherein, R¹ represents NR⁴R⁵ or a 1C-5Calkyl group; R²and R⁴ each represent a 1C-5C alkyl group or hydrogenatom; and R³ and R⁵ each represent a 1C-5C alkyl group); or (b)HSiCI(NR¹R²)(NR³R⁴), wherein R¹ and R³ independently represent an alkylgroup having 1 to 4 carbon atoms, or a hydrogen atom; and R² and R⁴independently represent an alkyl group having 1 to 4 carbon atoms. Theorganic silicon compounds contained H—Si bonds.

U.S. Pat. No. 5,424,095 describes a method to reduce the rate of cokeformation during the industrial pyrolysis of hydrocarbons, the interiorsurface of a reactor is coated with a uniform layer of a ceramicmaterial, the layer being deposited by thermal decomposition of anon-alkoxylated organosilicon precursor in the vapor phase, in a steamcontaining gas atmosphere in order to form oxide ceramics.

U.S. 2012/0291321 describes a PECVD process for forming a high-qualitySi carbonitride barrier dielectric film between a dielectric film and ametal interconnect of an integrated circuit substrate, comprising thesteps of: providing an integrated circuit substrate having a dielectricfilm or a metal interconnect; contacting the substrate with a barrierdielectric film precursor comprising: R_(x)R_(y)(NRR′)_(z)Si wherein R,R′, R and R′ are each individually selected from H, linear or branchedsaturated or unsaturated alkyl, or aromatic group; wherein x+y+z=4; z=1to 3; but R, R′ cannot both be H; and where z=1 or 2 then each of x andy are at least 1; forming the Si carbonitride barrier dielectric filmwith C/Si ratio>0.8 and a N/Si ratio >0.2 on the integrated circuitsubstrate.

U.S. 2013/0295779 A describes an atomic layer deposition (ALD) processfor forming a silicon oxide film at a deposition temperature >500° C.using silicon precursors having the following formula:

I. R¹R² _(m)Si(NR³R⁴)_(n)X_(p)   I.

wherein R¹, R², and R³ are each independently selected from hydrogen, alinear or branched C₁ to C₁₀ alkyl group, and a C₆ to C₁₀ aryl group; R⁴is selected from, a linear or branched C₁ to C₁₀ alkyl group, and a C₆to C₁₀ aryl group, a C₃ to C₁₀ alkylsilyl group; wherein R³ and R⁴ arelinked to form a cyclic ring structure or R³ and R⁴ are not linked toform a cyclic ring structure; X is a halide selected from the groupconsisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; and p is 0 to 2and m+n+p=3; and

R¹R² _(m)Si(OR³)_(n)(OR⁴)_(q)X_(p)   II.

wherein R¹ and R² are each independently selected from hydrogen, alinear or branched C₁ to C₁₀ alkyl group, and a C₆ to C₁₀ aryl group; R³and R⁴ are each independently selected from a linear or branched C₁ toC₁₀ alkyl group, and a C₆ to C₁₀ aryl group; wherein R³ and R⁴ arelinked to form a cyclic ring structure or R³ and R⁴ are not linked toform a cyclic ring structure; X is a halide atom selected from the groupconsisting of Cl, Br and 1; m is 0 to 3; n is 0 to 2; q is 0 to 2 and pis 0 to 2 and m+n+q+p=3

U.S. Pat. No. 7,084,076 discloses a halogenated siloxane such ashexachlorodisiloxane (HCDSO) that is used in conjunction with pyridineas a catalyst for ALD deposition below 500° C. to form silicon dioxide.

U.S. Pat. No. 6,992,019 discloses a method for catalyst-assisted atomiclayer deposition (ALD) to form a silicon dioxide layer having superiorproperties on a semiconductor substrate by using a first reactantcomponent consisting of a silicon compound having at least two siliconatoms, or using a tertiary aliphatic amine as the catalyst component, orboth in combination, together with related purging methods andsequencing. The precursor used is hexachlorodisilane. The depositiontemperature is between 25-150° C.

WO 2015/0105337 discloses novel trisilyl amine derivatives and a methodfor formation of silicon-containing thin films, wherein the trisilylamine derivatives are having thermal stability, high volatility, andhigh reactivity and being present in a liquid state at room temperatureand under pressure where handling is possible, may form a high puritysilicon-containing thin film having excellent physical and electricproperties by various deposition methods.

WO 2015/0190749 discloses novel amino-silyl amine compounds,(Me₂NSiR³R⁴)N(SiHR¹R²)₂ (R¹-R⁴=R₁₋₃ alkyl, C₂₋₃ alkenyl, C₂₋₃ alkynyl,C₃₋₇ cycloalkyl, C₆₋₁₂ aryl, etc.), and a method of a dielectric filmcontaining Si—N bond. Since the amino-silyl amine compd. according tothe present invention, which is a thermally stable and highly volatilecompd., may be treated at room temp. and used as a liq. state compd. atroom temp. and pressure, the present invention provides a method of ahigh purity dielectric film containing a Si—N bond even at a low temp.and plasma condition by using at. layer deposition (PEALD).

U.S. Pat. No. 9,245,740 provides novel amino-silyl amine compounds, amethod for preparing the same, and a silicon-containing thin-film usingthe same, wherein the amino-silyl amine compd. has thermal stability andhigh volatility and is maintained in a liquid state at room temp. andunder a pressure where handling is easy to thereby form asilicon-containing thin-film having high purity and excellent physicaland electric properties by various deposition methods.

U.S. 2015/0376211A discloses mono-substituted TSA precursorSi-containing film forming compositions are disclosed. The precursorshave the formula: (SiH₃)₂N—SiH₂—X, wherein X is selected from a halogenatom; an isocyanato group; an amino group; an N-containing C₄-C₁₀saturated or unsaturated heterocycle; or an alkoxy group. Methods forforming the Si-containing film using the disclosed mono-substituted TSAprecursor are also disclosed.

Despite these developments, there is still a need for a process forforming a silicon oxide film having at least one or more of thefollowing attributes: a density of about 2.1 g/cc or greater, a growthrate of 1.5 Å/cycle or greater, low chemical impurity, and/or highconformality in a thermal atomic layer deposition, a plasma enhancedatomic layer deposition (ALD) process or a plasma enhanced ALD-likeprocess using cheaper, reactive, and more stable silicon precursorcompounds. In addition, there is a need to develop precursors that canprovide tunable films for example, ranging from silicon oxide to carbondoped silicon oxide.

BRIEF SUMMARY OF THE INVENTION

Described herein is a process for the deposition of a stoichiometric ornonstoichiometric silicon oxide or silicon nitride material or film,such as without limitation, a silicon oxide, a carbon doped siliconoxide, a silicon oxynitride film, a carbon doped silicon oxynitridefilm, a silicon nitride film, or a carbon doped silicon nitride film atrelatively low temperatures, e.g., at one or more temperatures of 600°C. or lower, in a plasma enhanced ALD, plasma enhanced cyclic chemicalvapor deposition (PECCVD), a plasma enhanced ALD-like process, or an ALDprocess with oxygen reactant source.

In one aspect, there is provided method for depositing a film comprisingsilicon oxide onto a substrate which comprises the steps of:

-   -   a) providing a substrate in a reactor;    -   b) introducing into the reactor at least one silicon precursor        compound comprising a trisilylamine derivative compound, wherein        the trisilylamine derivative compound is selected from the group        consisting of Formulae A and B:

-   -   wherein R¹ is selected from the group consisting of a C₃ to C₁₀        cyclic alkyl group, a branched C₄ to C₁₀ cyclic alkyl group, a        C₃ to C₁₀ cyclic alkenyl group, a branched C₄ to C₁₀ cyclic        alkenyl group, a C₃ to C₆ cyclic alkynyl group, and a branched        C₃ to C₆ cyclic alkynyl group; R and R²⁻⁸ are each independently        selected from the group consisting of hydrogen, a linear or        branched C₁ to C₁₀ alkyl group, a linear or branched C₃ to C₁₀        alkenyl group, a linear or branched C₃ to C₁₀ alkynyl group, a        C₁ to C₆ dialkylamino group, a C₁ to C₆ alkylamino group, a C₆        to C₁₀ aryl group, a C₃ to C₁₀ cyclic alkyl group, a branched C₄        to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclic alkenyl group, a        branched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆ cyclic        alkynyl group, a branched C₃ to C₆ cyclic alkynyl group, and a        C₄ to C₁₀ aryl group;    -   c) purging the reactor with a purge gas;    -   d) introducing an oxygen-containing source into the reactor; and    -   e) purging the reactor with the purge gas,    -   wherein the steps b through e are repeated until a desired        thickness of film is deposited; and wherein the method is        conducted at one or more temperatures ranging from about 25° C.        to 600° C.

In some embodiments, the oxygen-containing source is a source selectedfrom the group consisting of an oxygen plasma, ozone, a water vapor,water vapor plasma, nitrogen oxide (e.g., N₂O, NO, NO₂) plasma with orwithout inert gas, hydrogen peroxide (H₂O₂), a carbon oxide (e.g., CO₂,CO) plasma and combinations thereof. In certain embodiments, the oxygensource further comprises an inert gas. In these embodiments, the inertgas is selected from the group consisting of argon, helium, nitrogen,hydrogen, and combinations thereof. In an alternative embodiment, theoxygen source does not comprise an inert gas. In yet another embodiment,the oxygen-containing source comprises nitrogen which reacts with thereagents under plasma conditions to provide a silicon oxynitride film.

In one or more embodiments described above, the oxygen-containing plasmasource is selected from the group consisting of oxygen plasma with orwithout inert gas, water vapor plasma with or without inert gas,nitrogen oxides (N₂O, NO, NO₂) plasma with or without inert gas, carbonoxides (CO₂, CO) plasma with or without inert gas, and combinationsthereof. In certain embodiments, the oxygen-containing plasma sourcefurther comprises an inert gas. In these embodiments, the inert gas isselected from the group consisting of argon, helium, nitrogen, hydrogen,or combinations thereof. In an alternative embodiment, theoxygen-containing plasma source does not comprise an inert gas.

One embodiment of the invention relates to a composition for depositinga film selected from a silicon oxide or a carbon doped silicon oxidefilm using a vapor deposition process, the trisilylamine derivativecompound is selected from the group consisting of Formulae A and B:

wherein R¹ is selected from a C₃ to C₁₀ cyclic alkyl group, a branchedC₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclic alkenyl group, abranched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆ cyclic alkynylgroup, and a branched C₃ to C₆ cyclic alkynyl group; R and R²⁻⁸ are eachindependently selected from the group consisting of hydrogen, a linearor branched C₁ to C₁₀ alkyl group, a linear or branched C₃ to C₁₀alkenyl group, a linear or branched C₃ to C₁₀ alkynyl group, a C₁ to C₆dialkylamino group, a C₁ to C₆ alkylamino group, a C₆ to C₁₀ aryl group,a C₃ to C₁₀ cyclic alkyl group, a branched C₄ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ cyclic alkenyl group, a branched C₄ to C₁₀ cyclic alkenylgroup, a C₃ to C₆ cyclic alkynyl group, a branched C₃ to C₆ cyclicalkynyl group, and a C₄ to C₁₀ aryl group.

Another embodiment of the invention relates to a silicon oxide filmcomprising at least one of the following characteristics a density of atleast about 2.1 g/cc; a wet etch rate that is less than about 2.5 Å/s asmeasured in a solution of 1:100 of HF to water dilute HF (0.5 wt % dHF)acid; an electrical leakage of less than about 1 e-8 A/cm² up to 6MV/cm; and a hydrogen impurity of less than about 5 e20 at/cc asmeasured by SIMS.

The embodiments of the invention can be used alone or in combinationswith each other.

DETAILED DESCRIPTION OF THE INVENTION

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

Described herein are methods related to the formation of astoichiometric or nonstoichiometric film or material comprising siliconand oxygen such as, without limitation, a silicon oxide, a carbon-dopedsilicon oxide film, a silicon oxynitride, a carbon-doped siliconoxynitride films or combinations thereof with one or more temperatures,of about 600° C. or less, or from about 25° C. to about 600° C. Thefilms described herein are deposited in a deposition process such as anatomic layer deposition (ALD) or in an ALD-like process such as, withoutlimitation, a plasma enhanced ALD or a plasma enhanced cyclic chemicalvapor deposition process (CCVD). The low temperature deposition (e.g.,one or more deposition temperatures ranging from about ambienttemperature to 600° C.) methods described herein provide films ormaterials that exhibit at least one or more of the following advantages:a density of about 2.1 g/cc or greater, low chemical impurity, highconformality in a thermal atomic layer deposition, a plasma enhancedatomic layer deposition (ALD) process or a plasma enhanced ALD-likeprocess, an ability to adjust carbon content in the resulting film;and/or films have an etching rate of 5 Angstroms per second (Å/sec) orless when measured in 0.5 wt % dilute HF. For carbon-doped silicon oxidefilms, greater than 1% carbon is desired to tune the etch rate to valuesbelow 2 Å/sec in 0.5 wt % dilute HF in addition to other characteristicssuch as, without limitation, a density of about 1.8 g/cc or greater orabout 2.0 g/cc or greater.

The present invention can be practiced using equipment known in the art.For example, the inventive method can use a reactor that is conventionalin the semiconductor manufacturing art.

In one aspect, the silicon precursor described herein comprises at leastone trisilylamine derivative compound having at least one SiH_(x) (x=1or 2) group connected to an organoamino functionality. Such siliconprecursor has a structure that is selected from the group consisting ofFormulae A and B below:

wherein R¹ is selected from a C₃ to C₁₀ cyclic alkyl group, a branchedC₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclic alkenyl group, abranched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆ cyclic alkynylgroup, a branched C₃ to C₆ cyclic alkynyl group; R and R²⁻⁸ are eachindependently selected from the group consisting of hydrogen, a linearor branched C₁ to C₁₀ alkyl group, a linear or branched C₃ to C₁₀alkenyl group, a linear or branched C₃ to C₁₀ alkynyl group, a C₁ to C₆dialkylamino group, a C₁ to C₆ alkylamino group, a C₆ to C₁₀ aryl group,a C₃ to C₁₀ cyclic alkyl group, a branched C₄ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ cyclic alkenyl group, a branched C₄ to C₁₀ cyclic alkenylgroup, a C₃ to C₆ cyclic alkynyl group, a branched C₃ to C₆ cyclicalkynyl group, and a C₄ to C₁₀ aryl group.

In another aspect, there is provided a composition comprising: (a) atleast one trisilylamine derivative compound having at least one SiH_(x)(x=1 or 2) group connected to an organoamino functionality. Suchtrisilylamine derivative compound is selected from the group consistingof Formulae A and B:

wherein R¹ is selected from a C₃ to C₁₀ cyclic alkyl group, a branchedC₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclic alkenyl group, abranched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆ cyclic alkynylgroup, a branched C₃ to C₆ cyclic alkynyl group; R and R²⁻⁸ are eachindependently selected from the group consisting of hydrogen, a linearor branched C₁ to C₁₀ alkyl group, a linear or branched C₃ to C₁₀alkenyl group, a linear or branched C₃ to C₁₀ alkynyl group, a C₁ to C₆dialkylamino group, a C₁ to C₆ alkylamino group, a C₆ to C₁₀ aryl group,a C₃ to C₁₀ cyclic alkyl group, a branched C₄ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ cyclic alkenyl group, a branched C₄ to C₁₀ cyclic alkenylgroup, a C₃ to C₆ cyclic alkynyl group, a branched C₃ to C₆ cyclicalkynyl group, and a C₄ to C₁₀ aryl group; and (b) a solvent.

In certain embodiments of the composition described herein, exemplarysolvents can include, without limitation, ether, tertiary amine, alkylhydrocarbon, aromatic hydrocarbon, tertiary aminoether, and combinationsthereof. In certain embodiments, the difference between the boilingpoint of the at least one trisilylamine deriviative compound and theboiling point of the solvent is 40° C. or less.

In another embodiment of the present invention, a method is describedherein for depositing a silicon oxide film on at least one surface of asubstrate, wherein the method comprises the steps of:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor at least one silicon precursor        selected from the group consisting of Formulae A and B herein;    -   c. purging the reactor with purge gas;    -   d. introducing oxygen-containing source comprising a plasma into        the reactor; and    -   e. purging the reactor with a purge gas.

In this method, steps b through e are repeated until a desired thicknessof film is deposited on the substrate.

The method of the present invention is conducted via an ALD process thatuses ozone or an oxygen-containing source which comprises a plasmawherein the plasma can further comprise an inert gas such as one or moreof the following: an oxygen plasma with or without inert gas, a watervapor plasma with or without inert gas, a nitrogen oxide (e.g., N₂O, NO,NO₂) plasma with or without inert gas, a carbon oxide (e.g., CO₂, CO)plasma with or without inert gas, and combinations thereof.

The oxygen-containing plasma source can be generated in situ or,alternatively, remotely. In one particular embodiment, theoxygen-containing source comprises oxygen and is flowing, or introducedduring method steps b through d, along with other reagents such aswithout limitation, the at least one silicon precursor and optionally aninert gas.

In one or more embodiments, the at least one silicon precursor comprisesat least one trisilylamine derivative compound having a structurerepresented by Formula A as defined above. In one particular embodiment,R and R²⁻⁸ in the Formula A comprise a hydrogen or C₁ alkyl group ormethyl. Further exemplary precursors are listed in Table 1.

TABLE 1 Trisilylamine Derivative Compounds of Formula A

In other embodiments, the at least one silicon precursor comprises atleast one trisilylamine derivative compound having a structurerepresented by Formula B as defined above. Further exemplary precursorsare listed in Table 2.

TABLE 2 Trisilylamine Derivative Compounds of Formula B

In the formulae above and throughout the description, the term “alkyl”denotes a linear or branched functional group having from 1 to 10 carbonatoms. Exemplary linear alkyl groups include, but are not limited to,methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Exemplarybranched alkyl groups include, but are not limited to, iso-propyl,iso-butyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, iso-hexyl,and neo-hexyl. In certain embodiments, the alkyl group may have one ormore functional groups attached thereto such as, but not limited to, analkoxy group, a dialkylamino group or combinations thereof, attachedthereto. In other embodiments, the alkyl group does not have one or morefunctional groups attached thereto. The alkyl group may be saturated or,alternatively, unsaturated.

In the formulae above and throughout the description, the term “cyclicalkyl” denotes a cyclic functional group having from 4 to 10 carbonatoms. Exemplary cyclic alkyl groups include, but are not limited to,cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

In the formulae above and throughout the description, the term “alkenylgroup” denotes a group which has one or more carbon-carbon double bondsand has from 2 to 10 or from 2 to 10 or from 2 to 6 carbon atoms.

In the formulae above and throughout the description, the term “alkynylgroup” denotes a group which has one or more carbon-carbon triple bondsand has from 3 to 10 or from 2 to 10 or from 2 to 6 carbon atoms.

In the formulae described herein and throughout the description, theterm “dialkylamino group or alkylamino group” denotes a group which hastwo alkyl groups bonded to a nitrogen atom or one alkyl bonded to anitrogen atom and has from 1 to 10 or from 2 to 6 or from 2 to 4 carbonatoms. Example include but not limited to HNMe, HNBu^(t), NMe₂, NMeEt,NEt₂, NPr^(i) ₂.

In the formulae above and throughout the description, the term “aryl”denotes an aromatic cyclic functional group having from 4 to 10 carbonatoms, from 5 to 10 carbon atoms, or from 6 to 10 carbon atoms.Exemplary aryl groups include, but are not limited to, phenyl, benzyl,chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrrolyl, and furanyl.

Compounds of Formulas A and B can be produced by following reactionequations (1) to (3):

The reaction in Equations (1) to (3) can be conducted with (e.g., in thepresence of) or without (e.g., in the absence of) organic solvents. Inembodiments wherein an organic solvent is used, examples of suitableorganic solvents include, but are not limited to, hydrocarbon such ashexanes, octane, toluene, and ethers such as diethyl ether andtetrahydrofuran (THF). In these or other embodiments, the reactiontemperature is in the range of from about −70° C. to the boiling pointof the solvent employed if a solvent is used. The resulting siliconprecursor compound can be purified, for example, via vacuum distillationafter removing all by-products as well as any solvent(s) if present.

Equations (1) and (3) are exemplary synthetic routes to make the siliconprecursor compound having Formulae A or B involving a reaction betweenhalidotrisilylamine or trisilyamine and a primary or secondary amine asdescribed in literatures. Other synthetic routes may be also employed tomake these silicon precursor compounds having Formulae A or B asdisclosed in the prior art.

The catalyst employed in the method of the present invention is one thatpromotes the formation of a silicon-nitrogen bond, i.e. dehydro-couplingin equations (2) or (3). Exemplary catalysts that can be used with themethod described herein include, but are not limited to the following:alkaline earth metal catalysts; halide-free main group, transitionmetal, lanthanide, and actinide catalysts; and halide-containing maingroup, transition metal, lanthanide, and actinide catalysts.

Exemplary alkaline earth metal catalysts include but are not limited tothe following: Mg[N(SiMe₃)₂]₂, MgR₂ (R=alkyl such as n-butyl, n-propyl,Et), To^(M)MgMe [To^(M)=tris(4,4-dimethyl-2-oxazolinyl)phenylborate],To^(M)Mg—H, To^(M)Mg—NR₂ (R═H, alkyl, aryl) Ca[N(SiMe₃)₂]₂,dibenzylcalcium, di-n-butylmagnesium, [(dipp-nacnac)CaX(THF)]₂(dipp-nacnac=CH[(CMe)(2,6-^(i)Pr₂-C₆H₃N)]₂; X═H, alkyl, carbosilyl,organoamino), Ca(CH₂Ph)₂, Ca(C₃H₅)₂, Ca(α-Me₃Si-2-(Me₂N)-benzyl)₂(THF)₂,Ca(9-(Me₃Si)-fluorenyl)(α-Me₃Si-2-(Me₂N)-benzyl)(THF),[(Me₃TACD)₃Ca₃(μ³-H)₂]⁺ (Me₃TACD=Me₃[12]aneN₄), Ca(η²-Ph₂CNPh)(hmpa)₃(hmpa=hexamethylphosphoramide), Sr[N(SiMe₃)₂]₂, and other M²⁺ alkalineearth metal-amide, -imine, -alkyl, -hydride, and -carbosilyl complexes(M=Ca, Mg, Sr, Ba).

Exemplary halide-free, main group, transition metal, lanthanide, andactinide catalysts include but are not limited to the following:1,3-di-iso-propyl-4,5-dimethylimidazol-2-ylidene, 2,2′-bipyridyl,phenanthroline, B(C₆F₅)₃, BR₃ (R=linear, branched, or cyclic C₁ to C₁₀alkyl group, a C₅ to C₁₀ aryl group, or a C₁ to C₁₀ alkoxy group), AIR₃(R=linear, branched, or cyclic C₁ to C₁₀ alkyl group, a C₅ to C₁₀ arylgroup, or a C₁ to C₁₀ alkoxy group), (C₅H₅)₂TiR₂ (R=alkyl, H, alkoxy,organoamino, carbosilyl), (C₅H₅)₂Ti(OAr)₂ [Ar=(2,6-(^(i)Pr)₂C₆H₃)],(C₅H₅)₂Ti(SiHRR′)PMe₃ (wherein R, R′ are each independently selectedfrom H, Me, Ph), TiMe₂(dmpe)₂ (dmpe=1,2-bis(dimethylphosphino)ethane),bis(benzene)chromium(0), Cr(CO)₆, Mn₂(CO)₁₂, Fe(CO)₅, Fe₃(CO)₁₂,(C₅H₅)Fe(CO)₂Me, CO₂(CO)₈, Ni(II) acetate, Nickel(II) acetylacetonate,Ni(cyclooctadiene)₂, [(dippe)Ni(μ-H)]₂(dippe=1,2-bis(di-iso-propylphosphino)ethane), (R-indenyl)Ni(PR′₃)Me(R=1-^(i)Pr, 1-SiMe₃, 1,3-(SiMe₃)₂; R′=Me,Ph),[{Ni(η-CH₂:CHSiMe₂)₂O}{μ-(η-CH₂:CHSiMe₂)₂O}], Cu(I) acetate, CuH,[tris(4,4-dimethyl-2-oxazolinyl)phenylborate]ZnH, (C₅H₅)₂ZrR₂ (R=alkyl,H, alkoxy, organoamino, carbosilyl), Ru₃(CO)₁₂,[(Et₃P)Ru(2,6-dimesitylthiophenolate)][B[3,5-(CF₃)₂C₆H₃]₄],[(C₅Me₅)Ru(R₃P)_(x)(NCMe)_(3-x)]⁺ (wherein R is selected from a linear,branched, or cyclic C₁ to C₁₀ alkyl group and a C₅ to C₁₀ aryl group;x=0, 1, 2, 3), Rh₆(CO)₁₆, tris(triphenylphosphine)rhodium(I)carbonylhydride, Rh₂H₂(CO)₂(dppm)₂ (dppm=bis(diphenylphosphino)methane,Rh₂(p-SiRH)₂(CO)₂(dppm)₂ (R=Ph, Et, C₆H₁₃), Pd/C,tris(dibenzylideneacetone)dipalladium(0),tetrakis(triphenylphosphine)palladium(0), Pd(II) acetate, (C₅H₅)₂SmH,(C₅Me₅)₂SmH, (THF)₂Yb[N(SiMe₃)₂]₂, (NHC)Yb(N(SiMe₃)₂)₂[NHC=1,3-bis(2,4,6-trimethylphenyl) imidazol-2-ylidene)],Yb(η²-Ph₂CNPh)(hmpa)₃ (hmpa=hexamethylphosphoramide), W(CO)₆, Re₂(CO)₁₀,Os₃(CO)₁₂, Ir₄(CO)₁₂, (acetylacetonato)dicarbonyliridium(I), Ir(Me)₂(C₅Me₅)L (L=PMe₃, PPh₃), [Ir(cyclooctadiene)OMe]₂, PtO₂ (Adams'scatalyst), Pt/C, Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane(Karstedt's catalyst), bis(tri-tert-butylphosphine)platinum(0),Pt(cyclooctadiene)₂, [(Me₃Si)₂N]₃U][BPh₄], [(Et₂N)₃U][BPh₄], and otherhalide-free M^(n+) complexes (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn,Y, Zr, Nb, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho,Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, U; n=0, 1, 2, 3, 4, 5, 6).

Exemplary halide-containing, main group, transition metal, lanthanide,and actinide catalysts include but are not limited to the following: BX₃(X═F, Cl, Br, I), BF₃.OEt₂, AIX₃ (X═F, Cl, Br, I), (C₅H₅)₂TiX₂ (X═F,Cl), [Mn(CO)₄Br]₂, NiCl₂, (C₅H₅)₂ZrX₂ (X═F, Cl), PdCl₂, Pdl₂, CuCl, CuI,CuF₂, CuCl₂, CuBr₂, Cu(PPh₃)₃Cl, ZnCl₂, [(C₆H₆)RuX₂]₂ (X═Cl, Br, I),(Ph₃P)₃RhCl (Wilkinson's catalyst), [RhCl(cyclooctadiene)]₂,di-μ-chloro-tetracarbonyldirhodium(I), bis(triphenylphosphine)rhodium(I)carbonyl chloride, Ndl₂, Sml₂, Dyl₂, (POCOP)IrHCl(POCOP=2,6-(R₂PO)₂C₆H₃; R═^(i)Pr, ^(n)Bu, Me), H₂PtCl₆.nH₂O (Speier'scatalyst), PtCl₂, Pt(PPh₃)₂Cl₂, and other halide-containing M^(n+)complexes (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru,Rh, Pd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf,Ta, W, Re, Os, Ir, Pt, U; n=0, 1, 2, 3, 4, 5, 6).

In another aspect, the silicon precursor described herein comprises atleast one trisilylamine derivative compound having at least one SiH_(x)(x=1 or 2) group connected to a halido functionality. Such siliconprecursor has a structure that is selected from the group consisting ofFormula C below:

wherein X is a halido group selected from chloride (Cl), bromide (Br),and iodide (I); R and R³⁻⁸ are each independently selected from thegroup consisting of hydrogen, a linear or branched C₁ to C₁₀ alkylgroup, a linear or branched C₃ to C₁₀ alkenyl group, a linear orbranched C₃ to C₁₀ alkynyl group, a C₁ to C₆ dialkylamino group, a C₁ toC₆ alkylamino group, a C₆ to C₁₀ aryl group, a C₃ to C₁₀ cyclic alkylgroup, a branched C₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclicalkenyl group, a branched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆cyclic alkynyl group, a branched C₃ to C₆ cyclic alkynyl group, and a C₄to C₁₀ aryl group.

In yet another aspect, there is provided a composition comprising: (a)at least one trisilylamine derivative compound having at least oneSiH_(x) (x=1 or 2) group connected to a halido functionality. Suchtrisilylamine derivative compound is selected from the group consistingof Formula C:

wherein X is a halido group selected from chloride (Cl), bromide (Br),and iodide (I); R and R³⁻⁸ are each independently selected from thegroup consisting of hydrogen, a linear or branched C₁ to C₁₀ alkylgroup, a linear or branched C₃ to C₁₀ alkenyl group, a linear orbranched C₃ to C₁₀ alkynyl group, a C₁ to C₆ dialkylamino group, a C₁ toC₆ alkylamino group, a C₆ to C₁₀ aryl group, a C₃ to C₁₀ cyclic alkylgroup, a branched C₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclicalkenyl group, a branched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆cyclic alkynyl group, a branched C₃ to C₆ cyclic alkynyl group, and a C₄to C₁₀ aryl group; and (b) a solvent.

In one particular embodiment, R and R³⁻⁸ in the Formula C comprise ahydrogen or C₁ alkyl group or methyl. Further exemplary precursors arelisted in Table 3.

TABLE 3 Trisilylamine Derivative Compounds of Formula C

As shown in equation (1), the at least one trisilylamine derivativecompound having Formula C can be used as a reagent or precursor in thesynthesis of trisilylamine derivative compounds having Formula A,described herein. In addition to compounds having Formulae A or B, theat least one trisilylamine derivative compound having Formula C can beused as a precursor for the deposition of silicon-containing filmsincluding, but not limited to, a silicon oxide, a carbon doped siliconoxide, a silicon oxynitride film, a carbon doped silicon oxynitridefilm, a silicon nitride film, or a carbon doped silicon nitride film atrelatively low temperatures, e.g., at one or more temperatures of 600°C. or lower, in a plasma enhanced ALD, plasma enhanced cyclic chemicalvapor deposition (PECCVD), a plasma enhanced ALD-like process, or an ALDprocess with oxygen reactant source.

The silicon precursor compounds having Formulae A or B according to thepresent invention and compositions comprising the silicon precursorcompounds having Formulae A or B according to the present invention arepreferably substantially free of halide ions. As used herein, the term“substantially free” as it relates to halide ions (or halides) such as,for example, chlorides and fluorides, bromides, and iodides, means lessthan 5 ppm (by weight), preferably less than 3 ppm, and more preferablyless than 1 ppm, and most preferably 0 ppm as measured by ionchromatography (IC). Chlorides are known to act as decompositioncatalysts for the silicon precursor compounds having Formula A or B.Significant levels of chloride in the final product can cause thesilicon precursor compounds to degrade. The gradual degradation of thesilicon precursor compounds may directly impact the film depositionprocess making it difficult for the semiconductor manufacturer to meetfilm specifications. In addition, the shelf-life or stability isnegatively impacted by the higher degradation rate of the siliconprecursor compounds thereby making it difficult to guarantee a 1-2 yearshelf-life. Therefore, the accelerated decomposition of the siliconprecursor compounds presents safety and performance concerns related tothe formation of these flammable and/or pyrophoric gaseous byproducts.The silicon precursor compounds having Formulae A or B are preferablysubstantially free of metal ions such as , Li⁺, Mg²⁺, Al³⁺, Fe²⁺, Fe²⁺,Fe³⁺, Ni²⁺, Cr³⁺. As used herein, the term “substantially free” as itrelates to Li, Al, Fe, Ni, Cr means less than 5 ppm (by weight),preferably less than 3 ppm, and more preferably less than 1 ppm, andmost preferably 0.1 ppm as measured by inductively coupled plasma massspectrometry (ICP-MS). In some embodiments, the silicon precursorcompounds having Formulae A or B are free of metal ions such as , Li⁺,Mg²⁺, Al³⁺, Fe²⁺, Fe³⁺, Ni²⁺, Cr³⁺. As used herein, the term “free of”as it relates to Li, Mg, Al, Fe, Ni, Cr means 0 ppm (by weight) asmeasured by ICP-MS.

For those embodiments wherein the silicon precursor(s) having Formulae Aor B is (are) used in a composition comprising a solvent and a siliconprecursor compounds having Formulae A or B described herein, the solventor mixture thereof selected does not react with the silicon precursor.The amount of solvent by weight percentage in the composition rangesfrom 0.5 wt % by weight to 99.5 wt % or from 10 wt % by weight to 75 wt%. In this or other embodiments, the solvent has a boiling point (b.p.)similar to the b.p. of the silicon precursor of Formula A or B or thedifference between the b.p. of the solvent and the b.p. of the siliconprecursor of Formula A or B is 40° C. or less, 30° C. or less, or 20° C.or less, or 10° C. Alternatively, the difference between the boilingpoints ranges from any one or more of the following end-points: 0, 10,20, 30, or 40° C. Examples of suitable ranges of b.p. difference includewithout limitation, 0 to 40° C., 20° to 30° C., or 10° to 30° C.Examples of suitable solvents in the compositions include, but are notlimited to, an ether (such as 1,4-dioxane, dibutyl ether), a tertiaryamine (such as pyridine, 1-methylpiperidine, 1-ethylpiperidine,N,N′-Dimethylpiperazine, N,N,N′,N′-Tetramethylethylenediamine), anitrile (such as benzonitrile), an alkyl hydrocarbon (such as octane,nonane, dodecane, ethylcyclohexane), an aromatic hydrocarbon (such astoluene, mesitylene), a tertiary aminoether (such asbis(2-dimethylaminoethyl) ether), or mixtures thereof.

Throughout the description, the term “ALD or ALD-like” refers to aprocess including, but not limited to, the following processes: a) eachreactant including a silicon precursor and a reactive gas is introducedsequentially into a reactor such as a single wafer ALD reactor,semi-batch ALD reactor, or batch furnace ALD reactor; b) each reactantincluding the silicon precursor and the reactive gas is exposed to asubstrate by moving or rotating the substrate to different sections ofthe reactor and each section is separated by inert gas curtain, i.e.,spatial ALD reactor or roll to roll ALD reactor.

In certain embodiments, the silicon oxide or carbon doped silicon oxidefilms deposited using the methods described herein are formed in thepresence of oxygen-containing source comprising ozone, water (H₂O (e.g.,deionized water, purifier water, and/or distilled water), oxygen (O₂),oxygen plasma, NO, N₂O, NO₂, carbon monoxide (CO), carbon dioxide (CO₂)and combinations thereof. The oxygen-containing source is passedthrough, for example, either an in situ or remote plasma generator toprovide oxygen-containing plasma source comprising oxygen such as anoxygen plasma, a plasma comprising oxygen and argon, a plasma comprisingoxygen and helium, an ozone plasma, a water plasma, a nitrous oxideplasma, or a carbon dioxide plasma. In certain embodiments, theoxygen-containing plasma source comprises an oxygen source gas that isintroduced into the reactor at a flow rate ranging from about 1 to about2000 standard cubic centimeters (sccm) or from about 1 to about 1000sccm. The oxygen-containing plasma source can be introduced for a timethat ranges from about 0.1 to about 100 seconds. In one particularembodiment, the oxygen-containing plasma source comprises water having atemperature of 10° C. or greater. In embodiments wherein the film isdeposited by a PEALD or a plasma enhanced cyclic CVD process, theprecursor pulse can have a pulse duration that is greater than 0.01seconds (e.g., about 0.01 to about 0.1 seconds, about 0.1 to about 0.5seconds, about 0.5 to about 10 seconds, about 0.5 to about 20 seconds,about 1 to about 100 seconds) depending on the ALD reactor's volume, andthe oxygen-containing plasma source can have a pulse duration that isless than 0.01 seconds (e.g., about 0.001 to about 0.01 seconds).

The deposition methods disclosed herein may involve one or more purgegases. The purge gas, which is used to purge away unconsumed reactantsand/or reaction byproducts, is an inert gas that does not react with theprecursors. Exemplary purge gases include, but are not limited to, argon(Ar), nitrogen (N₂), helium (He), neon, hydrogen (H₂), and mixturesthereof. In certain embodiments, a purge gas such as Ar is supplied intothe reactor at a flow rate ranging from about 10 to about 2000 sccm forabout 0.1 to 1000 seconds, thereby purging the unreacted material andany byproduct that may remain in the reactor.

The respective step of supplying the precursors, oxygen source, and/orother precursors, source gases, and/or reagents may be performed bychanging the time for supplying them to change the stoichiometriccomposition of the resulting dielectric film.

Energy is applied to the at least one of the silicon precursor, oxygencontaining source, or combination thereof to induce reaction and to formthe dielectric film or coating on the substrate. Such energy can beprovided by, but not limited to, thermal, plasma, pulsed plasma, heliconplasma, high density plasma, inductively coupled plasma, X-ray, e-beam,photon, remote plasma methods, and combinations thereof. In certainembodiments, a secondary RF frequency source can be used to modify theplasma characteristics at the substrate surface. In embodiments whereinthe deposition involves plasma, the plasma-generated process maycomprise a direct plasma-generated process in which plasma is directlygenerated in the reactor, or alternatively, a remote plasma-generatedprocess in which plasma is generated outside of the reactor and suppliedinto the reactor.

The at least one silicon precursor may be delivered to the reactionchamber such as a plasma enhanced cyclic CVD or PEALD reactor or a batchfurnace type reactor in a variety of ways. In one embodiment, a liquiddelivery system may be utilized. In an alternative embodiment, acombined liquid delivery and flash vaporization process unit may beemployed, such as, for example, the turbo vaporizer manufactured by MSPCorporation of Shoreview, Minn., to enable low volatility materials tobe volumetrically delivered, which leads to reproducible transport anddeposition without thermal decomposition of the precursor. In liquiddelivery formulations, the precursors described herein may be deliveredin neat liquid form, or alternatively, may be employed in solventformulations or compositions comprising same. Thus, in certainembodiments the precursor formulations may include solvent component(s)of suitable character as may be desirable and advantageous in a givenend use application to form a film on a substrate.

As previously mentioned, the purity level of the at least one siliconprecursor is sufficiently high enough to be acceptable for reliablesemiconductor manufacturing. In certain embodiments, the at least onesilicon precursor described herein comprise less than 2% by weight, orless than 1% by weight, or less than 0.5% by weight of one or more ofthe following impurities: free amines, free halides or halogen ions, andhigher molecular weight species. Higher purity levels of the siliconprecursor described herein can be obtained through one or more of thefollowing processes: purification, adsorption, and/or distillation.

In one embodiment of the method described herein, a plasma enhancedcyclic deposition process such as PEALD-like or PEALD may be usedwherein the deposition is conducted using the at least one siliconprecursor and an oxygen plasma source. The PEALD-like process is definedas a plasma enhanced cyclic CVD process but still provides highconformal silicon oxide films.

In certain embodiments, the gas lines connecting from the precursorcanisters to the reaction chamber are heated to one or more temperaturesdepending upon the process requirements and the container of the atleast one silicon precursor is kept at one or more temperatures forbubbling. In other embodiments, a solution comprising the at least onesilicon precursor is injected into a vaporizer kept at one or moretemperatures for direct liquid injection.

A flow of argon and/or other gas may be employed as a carrier gas tohelp deliver the vapor of the at least one silicon precursor to thereaction chamber during the precursor pulsing. In certain embodiments,the reaction chamber process pressure is about 50 mTorr to 10 Torr. Inother embodiments, the reaction chamber process pressure can be up to760 Torr (e.g., about 50 mtorr to about 100 Torr).

In a typical PEALD or a PEALD-like process such as a PECCVD process, thesubstrate such as a silicon oxide substrate is heated on a heater stagein a reaction chamber that is exposed to the silicon precursor initiallyto allow the complex to chemically adsorb onto the surface of thesubstrate.

A purge gas such as argon purges away unabsorbed excess complex from theprocess chamber. After sufficient purging, an oxygen source may beintroduced into reaction chamber to react with the absorbed surfacefollowed by another gas purge to remove reaction by-products from thechamber. The process cycle can be repeated to achieve the desired filmthickness. In some cases, pumping can replace a purge with inert gas orboth can be employed to remove unreacted silicon precursors.

In this or other embodiments, it is understood that the steps of themethods described herein may be performed in a variety of orders, may beperformed sequentially, may be performed concurrently (e.g., during atleast a portion of another step), and any combination thereof. Therespective step of supplying the precursors and the oxygen source gasesmay be performed by varying the duration of the time for supplying themto change the stoichiometric composition of the resulting dielectricfilm. Also, purge times after precursor or oxidant steps can beminimized to <0.1 s so that throughput is improved.

In one particular embodiment, the method described herein deposits ahigh quality silicon oxide film on a substrate. The method comprises thefollowing steps:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor at least one silicon precursor        selected from the group consisting of Formulae A and B described        herein;    -   c. purging reactor with purge gas to remove at least a portion        of the unabsorbed precursors;    -   d. introducing an oxygen-containing plasma source into the        reactor and    -   e. purging reactor with purge gas to remove at least a portion        of the unreacted oxygen source,        wherein steps b through e are repeated until a desired thickness        of the silicon oxide film is deposited.

Yet another method disclosed herein forms a carbon doped silicon oxidefilm using a trisilylamine derivative compound having the chemicalstructure represented by Formula A or B as defined above plus an oxygensource.

A still further exemplary process is described as follows:

-   -   a. providing a substrate in a reactor;    -   b. contacting vapors generated from at least one trisilylamine        derivative compound selected from the group consisting of        Formulae A and B as defined above, with or without co-flowing an        oxygen source to chemically absorb the precursors on the heated        substrate;    -   c. purging away any unabsorbed precursors;    -   d. Introducing an oxygen source on the heated substrate to react        with the sorbed precursors; and,    -   e. purging away any unreacted oxygen source,        wherein steps b through e are repeated until a desired thickness        is achieved.

Various commercial ALD reactors such as single wafer, semi-batch, batchfurnace or roll to roll reactor can be employed for depositing the solidsilicon oxide or carbon doped silicon oxide.

Process temperature for the method described herein use one or more ofthe following temperatures as endpoints: 0, 25, 50, 75, 100, 125, 150,175, 200, 225, 250, 275, 300° C., 325° C., 350° C., 375° C., 400° C.,425° C., 450° C., 500° C., 525° C., 550° C. Exemplary temperature rangesinclude, but are not limited to the following: from about 0° C. to about300° C.; or from about 25° C. to about 300° C.; or from about 50° C. toabout 290° C.; or from about 25° C. to about 250° C., or from about 25°C. to about 200° C.

In another aspect, there is provided a method for depositing asilicon-containing film via flowable chemical vapor deposition (FCVD),the method comprising:

placing a substrate comprising a surface feature into a reactor whereinthe substrate is maintained at one or more temperatures ranging fromabout −20° C. to about 400° C. and a pressure of the reactor ismaintained at 100 torr or less;

introducing at least one compound selected from the group consisting ofFormulae A and B:

wherein R¹ is selected from a C₃ to C₁₀ cyclic alkyl group, a branchedC₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclic alkenyl group, abranched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆ cyclic alkynylgroup, a branched C₃ to C₆ cyclic alkynyl group; R and R²⁻⁸ are eachindependently selected from the group consisting of hydrogen, a linearor branched C₁ to C₁₀ alkyl group, a linear or branched C₃ to C₁₀alkenyl group, a linear or branched C₃ to C₁₀ alkynyl group, a C₁ to C₆dialkylamino group, a C₆ to C₁₀ aryl group, a C₃ to C₁₀ cyclic alkylgroup, a branched C₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclicalkenyl group, a branched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆cyclic alkynyl group, a branched C₃ to C₆ cyclic alkynyl group, and a C₄to C₁₀ aryl group;

providing an oxygen source into the reactor to react with the at leastone compound to form a film and cover at least a portion of the surfacefeature;

annealing the film at one or more temperatures of about 100° C. to 1000°C. to coat at least a portion of the surface feature; and

treating the substrate with an oxygen source at one or more temperaturesranging from about 20° C. to about 1000° C. to form a silicon-containingfilm on at least a portion of the surface feature.

In certain embodiments, the oxygen source is selected from the groupconsisting of water vapors, water plasma, ozone, oxygen, oxygen plasma,oxygen/helium plasma, oxygen/argon plasma, nitrogen oxides plasma,carbon dioxide plasma, hydrogen peroxide, organic peroxides, andmixtures thereof. In this or other embodiments, the method steps arerepeated until the surface features are filled with thesilicon-containing film. In embodiments wherein water vapor is employedas an oxygen source, the substrate temperature ranges from about −20° C.to about 40° C. or from about −10° C. to about 25° C.

In another embodiment, there is provided a method for depositing asilicon-containing film onto a substrate which comprises the steps of:providing a substrate in a reactor; introducing into the reactor atleast one silicon precursor compound comprising at least one siliconprecursor compound selected from the group consisting of Formulae A, B,and C:

wherein X is a halido group selected from chloride (Cl), bromide (Br),and iodide (I); R¹ is selected from a C₃ to C₁₀ cyclic alkyl group, abranched C₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclic alkenyl group,a branched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆ cyclic alkynylgroup, a branched C₃ to C₆ cyclic alkynyl group; R and R²⁻⁸ are eachindependently selected from the group consisting of hydrogen, a linearor branched C₁ to C₁₀ alkyl group, a linear or branched C₃ to C₁₀alkenyl group, a linear or branched C₃ to C₁₀ alkynyl group, a C₁ to C₆dialkylamino group, a C₁ to C₆ alkylamino group, a C₆ to C₁₀ aryl group,a C₃ to C₁₀ cyclic alkyl group, a branched C₄ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ cyclic alkenyl group, a branched C₄ to C₁₀ cyclic alkenylgroup, a C₃ to C₆ cyclic alkynyl group, a branched C₃ to C₆ cyclicalkynyl group, and a C₄ to C₁₀ aryl group; purging the reactor with apurge gas; introducing an oxygen-containing or nitrogen-containingsource (or combination thereof) into the reactor; and purging thereactor with the purge gas, wherein the steps are repeated until adesired thickness of film is deposited; and wherein the method isconducted at one or more temperatures ranging from about 25° C. to 600°C.

In some embodiments, the nitrogen-containing source may be introducedinto the reactor. Suitable nitrogen source gases may include, forexample, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine,nitrogen, nitrogen/hydrogen, nitrogen/argon plasma, nitrogen/heliumplasma, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma,organic amines such as tert-butylamine, dimethylamine, diethylamine,isopropylamine, diethylamine plasma, dimethylamine plasma,trimethylamine plasma, ethylenediamine plasma, an alkoxyamine such asethanolamine plasma and mixture thereof. In certain embodiments, thenitrogen-containing source comprises an ammonia plasma, a plasmacomprising nitrogen and argon, a plasma comprising nitrogen and heliumor a plasma comprising hydrogen and nitrogen source gas.

In another particular embodiment, the method described herein deposits ahigh quality silicon-containing film such as, for example, a siliconnitride film, on a substrate. The method comprises the following steps:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor at least one silicon precursor        having a structure selected from the group consisting of        Formulae A, B, and C described herein;    -   c. purging reactor with purge gas to remove at least a portion        of the unabsorbed precursors;    -   d. introducing a nitrogen-containing plasma source into the        reactor and    -   e. purging reactor with purge gas to remove at least a portion        of the unreacted nitrogen source,        wherein steps b through e are repeated until a desired thickness        of the silicon-containing film is deposited.

In a still further embodiment of the method described herein, the filmor the as-deposited film deposited from ALD, ALD-like, PEALD, PEALD-likeor FCVD is subjected to a treatment step (post deposition). Thetreatment step can be conducted during at least a portion of thedeposition step, after the deposition step, and combinations thereof.Exemplary treatment steps include, without limitation, treatment viahigh temperature thermal annealing; plasma treatment; ultraviolet (UV)light treatment; laser; electron beam treatment and combinations thereofto affect one or more properties of the film.

The films deposited with the silicon precursors having Formulae A, B, orC described herein, when compared to films deposited with previouslydisclosed silicon precursors under the same conditions, have improvedproperties such as, without limitation, a wet etch rate that is lowerthan the wet etch rate of the film before the treatment step or adensity that is higher than the density prior to the treatment step. Inone particular embodiment, during the deposition process, as-depositedfilms are intermittently treated. These intermittent or mid-depositiontreatments can be performed, for example, after each ALD cycle, afterevery a certain number of ALD, such as, without limitation, one (1) ALDcycle, two (2) ALD cycles, five (5) ALD cycles, or after every ten (10)or more ALD cycles.

In an embodiment wherein the film is treated with a high temperatureannealing step, the annealing temperature is at least 100° C. or greaterthan the deposition temperature. In this or other embodiments, theannealing temperature ranges from about 400° C. to about 1000° C. Inthis or other embodiments, the annealing treatment can be conducted in avacuum (<760 Torr), inert environment or in oxygen containingenvironment (such as H₂O, N₂O, NO₂ or O₂).

In an embodiment wherein the film is treated to UV treatment, film isexposed to broad band UV or, alternatively, an UV source having awavelength ranging from about 150 nanometers (nm) to about 400 nm. Inone particular embodiment, the as-deposited film is exposed to UV in adifferent chamber than the deposition chamber after a desired filmthickness is reached.

In an embodiment where in the film is treated with a plasma, passivationlayer such as SiO₂ or carbon doped SiO₂ is deposited to prevent chlorineand nitrogen contamination to penetrate into film in the subsequentplasma treatment. The passivation layer can be deposited using atomiclayer deposition or cyclic chemical vapor deposition.

In an embodiment wherein the film is treated with a plasma, the plasmasource is selected from the group consisting of hydrogen plasma, plasmacomprising hydrogen and helium, plasma comprising hydrogen and argon.Hydrogen plasma lowers film dielectric constant and boost the damageresistance to following plasma ashing process while still keeping thecarbon content in the bulk almost unchanged.

Without intending to be bound by a particular theory, it is believedthat the trisilylamine derivative compound having a chemical structurerepresented by Formulae A, B, and C as defined above can be anchored viareacting the organoamino group or a halido group with hydroxyl (—OH) ornitridized groups (═NH or —NH₂) on substrate surface to provide—SiHR—N(SiH₃)₂ fragments wherein the SiHR fragment is bonded to anitrogen atom having two or more silicon-containing groups, thusboosting the growth rate of silicon oxide or carbon doped silicon oxidecompared to conventional silicon precursors such asbis(tert-butylamino)silane or bis(diethylamino)silane having only onesilicon atom. In certain embodiments, it is preferred that R=hydrogen inFormulae A, B, and C such that the growth rate of the depositedsilicon-containing film can be maximized.

Without intending to be bound by a particular theory, it is alsobelieved that in certain embodiments employing trisilylamine derivativecompounds having Formula C, it is preferred that X═Br, and even morepreferred that X═I, since it is expected that the silicon-bromide groupwill be more reactive towards the substrate surface having NH or NH₂groups than silicon-chloride, and the silicon-iodide group is expectedto be even more reactive towards the substrate surface than eithersilicon-chloride or silicon-bromide.

Without intending to be bound by a particular theory, it is believedthat the trisilylamine derivative compound having a chemical structurerepresented by Formulae A or B or C as defined above can exhibit aunique and unanticipated balance between (a) reactivity towards thesubstrate surface during a deposition process and (b) intrinsic thermalstability of the compound itself such that it can be stored for extendedperiods without significant degradation and such that it does not reactwith itself at elevated temperatures to promote CVD reaction in adeposition process where self-limiting ALD or PEALD is desired. Forexample, a trisilylamine derivative of Formula A or B that isfunctionalized with the cyclopentylamino group (R¹=cyclopentyl) mayprove to have higher surface reactivity than an analog with theiso-propylamino group (R¹=iso-propyl). The two carbon atoms directlybound to the ipso carbon in the cyclopentylamino group are fused into aring and have limited motion (degrees of freedom). In contrast, the twoterminal methyl groups in the iso-propylamino group are not restrictedand can freely rotate, bend, and stretch such that they provide moresteric protection to the neighboring silicon atom, thus loweringreactivity with hydroxyl group at the substrate surface and limitinggrowth rate. Along these lines, a smaller alkylamino group such asethylamino or methylamino are likely to provide even higher reactivitywith the substrate surface, however, the thermal stability of thesederivatives may be too low, allowing intermolecular reaction anddegradation of the silicon precursor itself, which would be detrimentalto the deposition process. Therefore, in this example, thecyclopentylamino-functionalized trisilylamine shows improvedcharacteristics in the deposition process compared to iso-propylamino-or other branched alkylamino-functionalized trisilylamine analogswithout sacrificing intrinsic thermal stability of the trisilylaminederivative.

In certain embodiments, the silicon precursors having Formulae A, B, orC as defined above can also be used as a dopant for metal containingfilms, such as but not limited to, metal oxide films or metal nitridefilms. In these embodiments, the metal containing film is depositedusing an ALD or CVD process such as those processes described hereinusing metal alkoxide, metal amide, or volatile organometallicprecursors. Examples of suitable metal alkoxide precursors that may beused with the method disclosed herein include, but are not limited to,group 3 to 6 metal alkoxide, group 3 to 6 metal complexes having bothalkoxy and alkyl substituted cyclopentadienyl ligands, group 3 to 6metal complexes having both alkoxy and alkyl substituted pyrrolylligands, group 3 to 6 metal complexes having both alkoxy and diketonateligands; group 3 to 6 metal complexes having both alkoxy and ketoesterligands; Examples of suitable metal amide precursors that may be usedwith the method disclosed herein include, but are not limited to,tetrakis(dimethylamino)zirconium (TDMAZ),tetrakis(diethylamino)zirconium (TDEAZ),tetrakis(ethylmethylamino)zirconium (TEMAZ),tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium(TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH),tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium(TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), tert-butyliminotri(ethylmethylamino)tantalum (TBTEMT), ethyliminotri(diethylamino)tantalum (EITDET), ethyliminotri(dimethylamino)tantalum (EITDMT), ethyliminotri(ethylmethylamino)tantalum (EITEMT), tert-amyliminotri(dimethylamino)tantalum (TAIMAT), tert-amyliminotri(diethylamino)tantalum, pentakis(dimethylamino)tantalum,tert-amylimino tri(ethylmethylamino)tantalum,bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW),bis(tert-butylimino)bis(diethylamino)tungsten,bis(tert-butylimino)bis(ethylmethylamino)tungsten, and combinationsthereof. Examples of suitable organometallic precursors that may be usedwith the method disclosed herein include, but are not limited to, group3 metal cyclopentadienyls or alkyl cyclopentadienyls. Exemplary Group 3to 6 metals herein include, but not limited to, Y, La, Ce, Pr, Nd, Sm,Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W.

In certain embodiments, the silicon-containing films described hereinhave a dielectric constant of 6 or less, 5 or less, 4 or less, and 3 orless. In these or other embodiments, the films can a dielectric constantof about 5 or below, or about 4 or below, or about 3.5 or below.However, it is envisioned that films having other dielectric constants(e.g., higher or lower) can be formed depending upon the desired end-useof the film. An example of silicon-containing film that is formed usingthe silicon precursors having Formula A or B precursors and processesdescribed herein has the formulation Si_(x)O_(y)C_(z)N_(v)H_(w) whereinSi ranges from about 10% to about 40%; 0 ranges from about 0% to about65%; C ranges from about 0% to about 75% or from about 0% to about 50%;N ranges from about 0% to about 75% or from about 0% to 50%; and Hranges from about 0% to about 50% atomic percent weight % whereinx+y+z+v+w=100 atomic weight percent, as determined for example, by XPSor other means. Another example of the silicon-containing film that isformed using the trisilylamine derivative precursors of Formulae A, B,and C and processes described herein is silicon carbonitride wherein thecarbon content is from 1 at % to 80 at % measured by XPS. In yet,another example of the silicon-containing film that is formed using thetrisilylamine derivative precursors having Formula A and B and processesdescribed herein is amorphous silicon wherein both sum of nitrogen andcarbon contents is <10 at %, preferably <5 at %, most preferably <1 at %measured by XPS.

As mentioned previously, the method described herein may be used todeposit a silicon-containing film on at least a portion of a substrate.Examples of suitable substrates include but are not limited to, silicon,germanium doped silicon, germanium, boron doped silicon, SiO₂, Si₃N₄,OSG, FSG, silicon carbide, hydrogenated silicon carbide, siliconnitride, hydrogenated silicon nitride, silicon carbonitride,hydrogenated silicon carbonitride, boronitride, antireflective coatings,photoresists, germanium, germanium-containing, boron-containing, Ga/As,a flexible substrate, organic polymers, porous organic and inorganicmaterials, metals such as copper and aluminum, and diffusion barrierlayers such as but not limited to TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, orWN. The films are compatible with a variety of subsequent processingsteps such as, for example, chemical mechanical planarization (CMP) andanisotropic etching processes.

The deposited films have applications, which include, but are notlimited to, computer chips, optical devices, magnetic informationstorages, coatings on a supporting material or substrate,microelectromechanical systems (MEMS), nanoelectromechanical systems,thin film transistor (TFT), light emitting diodes (LED), organic lightemitting diodes (OLED), IGZO, and liquid crystal displays (LCD).Potential use of resulting solid silicon oxide or carbon doped siliconoxide include, but not limited to, shallow trench insulation, interlayer dielectric, passivation layer, an etch stop layer, part of a dualspacer, and sacrificial layer for patterning.

The methods described herein provide a high quality silicon oxide orcarbon-doped silicon oxide film. The term “high quality” means a filmthat exhibits one or more of the following characteristics: a density ofabout 2.1 g/cc or greater, 2.2 g/cc or greater, 2.25 g/cc or greater; awet etch rate that is 2.5 Å/s or less, 2.0 Å/s or less, 1.5 Å/s or less,1.0 Å/s or less, 0.5 Å/s or less, 0.1 Å/s or less, 0.05 Å/s or less,0.01 Å/s or less as measured in a solution of 1:100 of HF to waterdilute HF (0.5 wt % dHF) acid, ; an electrical leakage of about 1 orless e-8 A/cm² up to 6 MV/cm); a hydrogen impurity of about 5 e20 at/ccor less as measured by SIMS; and combinations thereof. With regard tothe etch rate, a thermally grown silicon oxide film has 0.5 Å/s etchrate in 0.5 wt % Hf.

In certain embodiments, one or more silicon precursors having FormulaeA, B, or C described herein can be used to form silicon oxide films thatare solid and are non-porous or are substantially free of pores.

The following examples illustrate the method for synthesizing siliconprecursors having Formulae A, B, and C, and for depositingsilicon-containing films described herein and are not intended to limitit in any way.

EXAMPLES

Thermal Atomic Layer Deposition of silicon oxide films were performed ona laboratory scale ALD processing tool. The silicon precursor wasdelivered to the chamber by vapor draw. All gases (e.g., purge andreactant gas or precursor and oxygen source) were preheated to 100° C.prior to entering the deposition zone. Gases and precursor flow rateswere controlled with ALD diaphragm valves with high speed actuation. Thesubstrates used in the deposition were 12 inch long silicon strips. Athermocouple attached on the sample holder to confirm substratetemperature. Depositions were performed using ozone as oxygen sourcegas. Normal deposition process and parameters are shown in Table 4.Thickness and refractive indices of the films were measured using aFilmTek 2000SE ellipsometer by fitting the reflection data from the filmto a pre-set physical model (e.g., the Lorentz Oscillator model).

TABLE 4 Process for Thermal Atomic Layer Deposition of Silicon OxideFilms with Ozone as Oxygen Source on the Laboratory Scale ALD ProcessingTool. Step 1 6 sec Evacuate reactor <100 mT Step 2 variable Dose Siliconprecursor Reactor pressure duration typically <2 Torr Step 3 6 sec Purgereactor with nitrogen Flow 1.5 slpm N₂ Step 4 6 sec Evacuate reactor<100 mT Step 5 variable Dose oxygen source ozone duration Step 6 6 secPurge reactor with nitrogen Flow 1.5 slpm N₂

All plasma enhanced ALD (PEALD) was performed on a commercial stylelateral flow reactor (300 mm PEALD tool manufactured by ASM) equippedwith 27.1 MHz direct plasma capability with 3.5 mm fixed spacing betweenelectrodes. The laminar flow chamber design utilizes outer and innerchambers which have independent pressure settings. The inner chamber isthe deposition reactor in which all reactant gases (e.g. precursor,argon) were mixed in the manifold and delivered to the process reactor.Argon gas was used to maintain reactor pressure in the outer chamber.Precursors were liquids maintained at room temperature in stainlesssteel bubblers and delivered to the chamber with Ar carrier gas(typically set at 200 sccm flow). All depositions reported in this studywere done on native oxide containing Si substrates of 8-12 Ohm-cm.Thickness and refractive indices of the films were measured using aFilmTek 2000SE ellipsometer. The growth rate per cycle is calculated bydividing the measured thickness of resulting silicon oxide film by thenumber of total ALD/PEALD cycles. Wet etch rate (WER) measurements wereperformed by using 1:99 diluted hydrofluoric (HF) acid solution. Thermaloxide wafers were used as standard for each set of experiments toconfirm the etch solution's activity. The samples were all etched for 15seconds to remove any surface layer before starting to collect the bulkfilm's WER. A typical thermal oxide wafer wet etch rate for 1:99 dHFwater solution was 0.5 Å/s by this procedure.

Example 1 Synthesis ofN-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine; Formula A WhereinR¹=Cyclohexyl, R²═Me, R and R³⁻⁸ are all Hydrogen

Cyclohexylmethylamine was dropwise added to chlorotrisilylamine inhexanes and the resulting mixture is stirred for several hours.Filtration followed by vacuum distillation provided the desired product,N-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine. GC-MS showed thefollowing peaks: 218 (M+), 203 (M-15), 175, 164, 147, 133, 106, 74.

Example 2 Alternative Synthesis ofN-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine; Formula A WhereinR¹=Cyclohexyl, R²═Me, R and R³⁻⁸ are all Hydrogen

Triruthenium dodecacarbonyl solids (1 mol %) were added to a mixture ofCyclohexylmethylamine (1 equiv) and trisilylamine (2 equiv) and stirredat room temperature overnight, during which time hydrogen gas wasevolved. The reaction mixture was analyzed by GC-MS and found to containthe desired product, N-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine.

Example 3 Synthesis ofN-cyclohexylmethylaminosilyl-N,N′,N′-trisilyl-silanediarnine; Formula BWherein R¹=Cyclohexyl, R²═Me.

Triruthenium dodecacarbonyl solids (1 mol %) were added to a mixture ofCyclohexylmethylamine (1 equiv) and N,N′-disilyltrisilazane (2 equiv)and stirred at room temperature overnight, during which time hydrogengas was evolved. The reaction mixture was analyzed by GC-MS and found tocontain the desired product,N-cyclohexylmethylaminosilyl-N,N′,N′-trisilyl-silanediarnine. GC-MSshowed the following peaks: 293 (M+), 278 (M-15), 250, 222, 208, 190,178, 163, 149, 135, 115, 100, 83, 74.

Example 4 Synthesis of N-chlorosilyl-tetramethyldisilazane; Formula Cwherein R³═R⁴═R⁶═R⁷═Me and R═R⁵═R⁸=Hydrogen

Under the protection of nitrogen atmosphere, a 2.7 M solution ofn-butyllithium in hexanes was dropwise added to 1 equivalent of1,1,3,3-tetramethyldisilazane in diethyl ether at −20° C. whilestirring. The resulting solution was then added dropwise to a heptanesand diethyl ether solution of dichlorosilane (1.5 equivalents) at −20°C. while stirring. The resulting white slurry was filtered to remove thesolids and the filtrate was concentrated under reduced pressure. Thecrude product was purified by vacuum-distillation to yield the desiredproduct, N-chlorosilyl-tetramethyldisilazane, as a colorless liquid.GC-MS showed the following peaks: 196 (M-1), 182 (M-15), 166, 150, 136,116, 102, 86, 70.

Example 5 Synthesis ofN-cyclohexyl-N-methyl-N′,N′-bis(dimethylsilyl)-silanediamine; Formula Awherein R¹=Cyclohexyl, R²═Me, and R³═R⁴═R⁶═R⁷═Me and R═R⁵═R⁸=Hydrogen

Cyclohexylmethylamine is dropwise added toN-chlorosilyl-tetramethyldisilazane in hexanes and the resulting mixtureis stirred for several hours. Filtration followed by vacuum distillationprovides N-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine. GC-MS showedthe following peaks: 274 (M+), 259 (M-15), 231, 203, 189, 175, 162, 148,130, 116, 102, 86.

Examples 6-15 Synthesis of Additional Trisilylamine Derivative CompoundsHaving Formula A

Additional trisilylamine derivative compounds having Formula A were madevia similar fashion as Examples 1, 2 and 4 and were characterized bymass spectroscopy (MS). The molecular weight (MW), the structure, andcorresponding major MS fragmentation peaks of each trisilylaminederivative compound are provided in Table 5 to confirm theiridentification.

TABLE 5 Trisilylamine derivative compounds having Formula A. No.Precursor Name MW Structure MS Peaks 6 N-cyclopentyl- N′,N′-disilyl-silanediamine 190.47

190, 175, 161, 147, 133, 117, 106, 86, 72 7 N-cyclohexyl- N′,N′-disilyl-silanediamine 204.50

204, 189, 175, 161, 147, 133, 119, 106, 88,  72 8 N-cyclohexyl-N-ethyl-N′,N′- disilyl-silane- diamine 232.55

232, 217, 204, 175, 161, 147, 133, 119, 106, 84, 72 9 N-cyclohexyl-N-iso-propyl- N′,N′-disilyl- silanediamine 246.58

246, 231, 216, 204, 175, 161, 147, 133, 119, 106, 84,  72 10N,N-dicyclo- hexyl-N′,N′- disilyl-silane- diamine 286.64

286, 243, 216, 203, 187, 173, 159, 148, 133, 119, 106, 83, 72 11N-cyclopentyl- N′,N′-bis (dimethylsilyl)- silanediamine 246.58

246, 231, 217, 203, 189, 175, 161, 147, 131, 117, 103, 87, 74 12N-cyclohexyl- N′,N′-bis (dimethylsilyl)- silanediamine 260.60

260, 245, 231, 217, 203, 189, 175, 161, 143, 131, 117, 103, 87,  74 13N-cyclohexyl- N-ethyl-N′,N′- bis(dimethyl- silyl)- silanediamine 288.66

288, 273, 259, 245, 217, 203, 189, 172, 162, 148, 131, 117, 103, 87, 7414 N-cyclohexyl- N-iso-propyl- N′,N′-bis (dimethylsilyl)- silanediamine302.68

302, 287, 259, 243, 231, 217, 203, 189, 175, 162, 148, 131, 117, 103,84,  74 15 N,N-dicyclo- hexyl-N′,N′- bis(dimethyl- silyl)- silanediamine342.75

342, 328, 299, 287, 272, 259, 244, 229, 215, 201, 189, 175, 162, 148,131, 117, 103, 84, 73

Comparative Example 16a PEALD Silicon Oxide UsingBis(diethylamino)Silane (BDEAS) in Laminar Flow Reactor with 27.1 MHzplasma at 50° C.

Depositions were performed with BDEAS as silicon precursor and O₂ plasmaunder conditions as described above in Table 6. Precursor was deliveredto chamber with carrier gas Ar flow of 200 sccm. Steps b to e wererepeated many times to get a desired thickness of silicon oxide formetrology. The film deposition parameters and the film properties atdifferent deposition conditions are shown in Table 7. With precursorpulse of 4 seconds, reactor pressure at 3 Torr, plasma power of 200 Wand plasma time of 5 seconds, a GPC of 1.19 Å/cycle is obtained at 100°C. and 0.95 Å/cycle is obtained at 300° C.

TABLE 6 Process for PEALD Silicon Oxide Deposition in the CommercialLateral Flow PEALD Reactor withN-cyclohexyl-N-methyl-N′,N′-bis(dimethylsilyl)-silanediamine. Step aIntroduce Si wafer Deposition temperature = 100° C. to the reactor or300° C. b Introduce silicon Precursor delivery = variable secondsprecursor to the with 200 sccm Ar; reactor Process gas Argon flow = 300sccm Reactor pressure = 2 or 3 Torr c Purge silicon Argon flow = 300sccm precursor with inert Argon flow time = 10 seconds at 300° C. gas(argon) and 20 seconds at 100° C. Reactor pressure = 2 or 3 Torr dOxidation using Argon flow = 300 sccm plasma Oxygen flow = 100 sccmPlasma power = 200 W Plasma time = variable seconds Reactor pressure = 2or 3 Torr e Purge O₂ plasma Plasma off Argon flow = 300 sccm Argon flowtime = 2 seconds Reactor pressure = 2 or 3 Torr

TABLE 7 PEALD Silicon Oxide Film Deposition Parameters and DepositionGPC by Bis(diethylamino)silane (BDEAS) Dep Reactor Oxygen Oxygen GPC WERT Pressure Precursor Plasma Plasma (Å/ (Å/ (° C.) (Torr) flow (s) time(s) Power (W) cycle) RI second) 100 3 1 5 200 1.16 1.47 1.73 100 3 2 5200 1.18 1.47 1.75 100 3 4 5 200 1.19 1.47 1.75 100 3 8 5 200 1.21 1.471.75 100 2 4 5 400 1.13 1.47 1.22 100 2 4 5 100 1.29 1.47 2.15 300 3 1 2200 1.02 1.46 2.27 300 3 2 2 200 1.04 1.46 2.23 300 3 4 2 200 1.06 1.452.30 300 3 10 2 200 1.07 1.46 2.18 300 3 4 5 200 0.95 1.47 1.24

Example 16 PEALD Silicon Oxide UsingN-cyclohexyl-N-methyl-N′,N′-bis(dimethylsilyl)-silanediamine in LaminarFlow Reactor with 27.1 MHz Plasma

Depositions were performed withN-cyclohexyl-N-methyl-N′,N′-bis(dimethylsilyl)-silanediamine as siliconprecursor and 02 plasma under conditions as described in Table 6.Precursor was delivered to chamber with carrier gas Ar flow of 200 sccm.Steps b to e were repeated many times to get a desired thickness ofsilicon oxide for metrology. The film deposition parameters and the filmproperties at different deposition conditions are shown in Table 8. Agrowth rate of 3 Å/cycle is obtained at 100° C. and 2.5 Å/cycle isobtained at 300° C.

TABLE 8 PEALD Silicon Oxide Film Deposition Parameters and DepositionGrowth per Cycle (GPC) byN-cyclohexyl-N-methyl-N′,N′-bis(dimethylsilyl)-silanediamine Dep ReactorOxygen Oxygen GPC WER T Pressure Precursor Plasma Plasma (Å/ (Å/ (° C.)(Torr) flow (s) time (s) Power (W) cycle) RI second) 100 3 12 5 2003.035 1.45 3.64 100 2 12 5 400 2.820 1.46 2.24 100 2 12 5 200 3.010 1.463.30 100 2 12 10 200 2.875 1.46 2.40 100 2 12 20 200 2.740 1.45 1.90 3003 4 2 200 2.160 1.46 NA 300 3 8 2 200 2.390 1.45 NA 300 3 12 2 200 2.4801.44 3.78 300 2 12 5 400 2.185 1.45 1.42 300 2 12 5 200 2.350 1.44 2.60300 2 12 5 100 2.48 1.44 3.49 300 2 12 10 200 2.260 1.44 1.97 300 2 1220 200 2.140 1.45 1.38 300 3 12 5 200 2.465 1.43 3.11

As shown in Table 8, the GPC using from this invention is much higherthan that of BDEAS under same deposition conditions, demonstrating thatthe silicon precursors having Formulae A, B, and C are more suitable forfabrication of silicon oxide films in semi-conductor industry.

Example 17 PEALD Silicon Oxide UsingN-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine (Prophetic)

Depositions are performed in similar fashion as Example 16, except thatN-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine is used as the siliconprecursor, to provide silicon oxide film with a growth rate greater than2.5 Å/cycle.

Example 18 PEALD Silicon Nitride UsingN-chlorosilyl-tetramethyldisilazane and Ar/N₂ Plasma (Prophetic)

A silicon-containing film was deposited usingN-chlorosilyl-tetramethyldisilazane as the silicon precursor and Ar/N₂plasma. The silicon precursor is delivered from a container using 100sccm Ar carrier gas. The susceptor temperature is set to 300° C., andthe reactor is equipped with parallel plate in-situ electrodes. Plasmafrequency and power are 13.56 MHz and 200 W, respectively. Depositionprocess steps are carried out as described in Table 9, wherein steps bthrough e were repeated many times to get a desired thickness of siliconnitride for metrology.

TABLE 9 Process for PEALD Silicon Nitride Deposition in the CommercialLateral Flow PEALD Reactor with N-chlorosilyl-tetramethyldisilazane.Step a Introduce Si wafer Deposition temperature = 300° C. to thereactor b Introduce silicon Precursor pulse = 1 second precursor to theCarrier gas = 100 sccm Ar; reactor Process gas argon flow = 500 sccmReactor pressure = 2 Torr c Purge silicon Argon flow = 500 sccmprecursor with inert Argon flow time = 10 seconds gas (argon) Reactorpressure = 2 Torr d Nitridation Argon flow = 125 sccm using Ar/N₂ plasmaNitrogen flow = 375 sccm Plasma power = 200 Watts Plasma time = 5seconds Reactor pressure = 2 Torr e Purge Ar/N₂ plasma Plasma off Argonflow = 500 sccm Argon flow time = 10 seconds Reactor pressure = 2 Torr

1. A method to deposit a film comprising silicon and nitrogen onto asubstrate comprises steps of: a) providing a substrate in a reactor; b)introducing into the reactor at least one silicon precursor compound,wherein the at least one silicon precursor compound is selected from thegroup consisting of Formula C:

wherein X is a halido group selected from chloride (Cl), bromide (Br),and iodide (I); R and R³⁻⁸ are each independently selected from thegroup consisting of hydrogen, a linear or branched C₁ to C₁₀ alkylgroup, a linear or branched C₃ to C₁₀ alkenyl group, a linear orbranched C₃ to C₁₀ alkynyl group, a C₁ to C₆ dialkylamino group, a C₁ toC₆ alkylamino group, a C₆ to C₁₀ aryl group, a C₃ to C₁₀ cyclic alkylgroup, a branched C₄ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ cyclicalkenyl group, a branched C₄ to C₁₀ cyclic alkenyl group, a C₃ to C₆cyclic alkynyl group, a branched C₃ to C₆ cyclic alkynyl group, and a C₄to C₁₀ aryl group; c) purging the reactor with purge gas; d) introducinga nitrogen-containing source into the reactor; and e) purging thereactor with purge gas, wherein steps b through e are repeated until adesired thickness of film is deposited, and; wherein the method isconducted at one or more temperatures ranging from about 25° C. to 600°C.
 2. The method of claim 1, wherein the compound is selected from thegroup consisting of N-bromosilyl-tetramethyldisilazane,N-iodosilyl-tetramethyldisilazane,N-bromo(methyl)silyl-tetramethyldisilazane,N-iodo(methyl)silyl-tetramethyldisilazane,N-chlorosilyl-hexamethyldisilazane, N-bromosilyl-hexamethyldisilazane,N-iodosilyl-hexamethyldisilazane,N-bromo(methyl)silyl-hexamethyldisilazane,N-iodo(methyl)silyl-hexamethyldisilazane.
 3. The method of claim 1,wherein the nitrogen-containing source is selected from the groupconsisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine,nitrogen, nitrogen/hydrogen, nitrogen/argon plasma, nitrogen/heliumplasma, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma,tert-butylamine, dimethylamine, diethylamine, isopropylamine,diethylamine plasma, dimethylamine plasma, trimethylamine plasma,ethylenediamine plasma, ethanolamine plasma, and mixtures thereof. 4.The method of claim 1 wherein a density of the film is about 2.1 g/cc orgreater.
 5. The method of claim 1 wherein the film further comprisescarbon and wherein a carbon content of the film is 0.5 atomic weightpercent (at. %) as measured by x-ray photospectroscopy or greater. 6.The method of claim 1 wherein a density of the film is about 1.8 g/cc orgreater.
 7. A composition for depositing a film selected from a siliconnitride or a carbon doped silicon nitride film using a vapor depositionprocess, the composition comprising: at least one silicon precursorcompound selected from the group consisting of Formula C as set forth inclaim
 1. 8. The composition of claim 7, wherein the silicon precursorcompound is selected from the group consisting ofN-bromosilyl-tetramethyldisilazane, N-iodosilyl-tetramethyldisilazane,N-bromo(methyl)silyl-tetramethyldisilazane,N-iodo(methyl)silyl-tetramethyldisilazane,N-chlorosilyl-hexamethyldisilazane, N-bromosilyl-hexamethyldisilazane,N-iodosilyl-hexamethyldisilazane,N-bromo(methyl)silyl-hexamethyldisilazane,N-iodo(methyl)silyl-hexamethyldisilazane and combinations thereof. 9.The composition of claim 7 wherein the halido group is selected from thegroup consisting of chloride, bromide, and iodide.